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Solid Acid-Catalyzed Dehydration/Beckmann Rearrangement of Aldoximes: Towards High Atom Efficiency Green Processes

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Solid Acid-Catalyzed Dehydration/Beckmann Rearrangement of Aldoximes: Towards High Atom Efficiency Green Processes Microporous and Mesoporous Materials 79 (2005) 21–27 www.elsevier.com/locate/micromeso Solid acid-catalyzed dehydration/Beckmann rearrangement of aldoximes: towards high atom efficiency green processes Bejoy Thomas, S. Prathapan, Sankaran Sugunan * Department of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, Kerala, India Received 23 August 2004; received in revised form 5 October 2004; accepted 7 October 2004 Available online 8 December 2004 Abstract Rare earth metal ion exchanged (La3+,Ce3+,RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehy- dration/Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at 473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration prod- uct (4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules. Ó 2004 Elsevier Inc. All rights reserved. Keywords: Acid amount; Beckmann rearrangement; Dehydration reaction; 4-Methoxyphenylformamide; Microporous materials; Rare earth exch- anged zeolites 1. Introduction amount of improvement is controlled by the extent of cation exchange [3,4]. These zeolites have been exten- Responsible care and sustainable development have sively used for industrial applications. Lanthanum ex- been the paradigms of industrial production. Therefore, changed Na-Y zeolite plays an important role in the the process has to be optimized in terms of energy effi- preparation of catalysts for fluid catalytic cracking, ciency, chemical utilization, and waste minimization one of the most widely applied petroleum refining pro- [1,2]. Solid acid catalysis is a growing field of research cesses that make use of zeolite catalyst components [4,5]. as the demand for clean and eco-friendly chemical pro- Nitriles are very important intermediates in synthetic cesses is increasing. Many organic reactions are known organic chemistry [6,7]. Many important multi-synthetic to be catalyzed by clays, ion-exchange resins and zeolites reactions pass through a nitrile intermediate. Examples both in natural and modified form [1]. include the synthesis of ibuprofen and ketoprofen; two The acid amount and thermal stability of synthetic widely used pharmaceutical agents that have variety of K-Y zeolite can be dramatically improved by ion uses [6,7]. Benzonitrile derivatives have been widely used exchanging with rare earth metal cations, and the as herbicides in agriculture [8]. Despite their wide appli- cability, preparation is a major concern. Aromatic * Corresponding author. Tel.: +91 484 2575804; fax: +91 484 hydrocarbons such as benzene, phenolic compounds or 2577595. phenyl ethers are cyanated using Cl3CCN, BrCN or E-mail address: [email protected] (S. Sugunan). mercury fulminate [Hg(ONC)2] [9,10]. These are special 1387-1811/$ - see front matter Ó 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2004.10.009 22 B. Thomas et al. / Microporous and Mesoporous Materials 79 (2005) 21–27 reagents. Their high cost, limited availability, sensitivity on zirconia and attains a value of about 80% during towards water and very low bio-degradability are major the ammoxidation of toluene [18]. Also, in many inves- concerns. Aliphatic nitriles are accessed through nucleo- tigations of the ammoxidation reactions studied, empha- philic substitution reactions of alkyl halides and tosy- sis was mostly placed on the examination of reaction lates with highly toxic cyanide ions as nucleophiles [7]. mechanism and catalyst development [19,20]. In the Two useful measures of the environmental impact of present paper we describe a convenient method for the chemical processes are the E-factor, defined by the mass preparation of nitriles through the dehydration of ratio of waste to desired product, and the atom utiliza- aldoximes (benzaldoxime and 4-methoxybenzaldoxime) tion, which is the ratio of the molecular weight of the de- over rare earth exchanged K-Y zeolites. Benzaldoxime sired product and molecular weights of all substances underwent only dehydration while 4-meth- produced in the stoichiometric equation. Processes oxybenzaldoxime both dehydration as well as Beck- employing acids and bases requiring neutralization, or mann rearrangement reactions. The activity-selectivity stoichiometric redox reagents, and toxic metal reagents results of rare earth exchanged zeolite catalysts are also represent the major sources of waste production in the comparable to those in the existing reports [13– form of salts and heavy metals and have high E-factors 18,21,22]. and low atom utilization as the catalysts are irreversibly lost. Low bio-degradability is a serious problem in these environmentally conscious days. The work-up of prod- 2. Experimental ucts from nitrations, sulphonations, cyanation, and many other acid-catalyzed reactions involves neutraliza- Potassium exchanged zeolite was prepared by ion ex- tion and the concomitant generation of inorganic wastes change of H-Y (Sud-Chemie-India, Si/Al = 1.5) at room such as NaCl, Na2SO4 and (NH4)2SO4 [1,2,11,12]. Green temperature with 0.1M KCl solution (0.05mol of KCl/g chemistry demands the replacement of these highly cor- of zeolite) for three times [23,24]. Rare earth exchanged rosive, hazardous and polluting acid catalysts with eco- zeolites were obtained by contacting K-Y with a 0.5M friendly solid acid catalysts. Hence, the idea of achieving respective nitrate solution (0.025mol of nitrate/g of zeo- chemical reaction that are economical, energy saving, lite, obtained from Indian Rare Earths Ltd. Udyog- safe and most importantly environmentally benign de- amandal, Kerala) at 353K for 24h [24,25]. All the mands some alternative for conventional catalysts. Het- samples were calcined after each exchange at tempera- erogeneous catalysis, long established in bulk-chemicals tures from 423 to 773K, and at 773K for 5h with a heat- processing, is beginning to make inroads into the fine- ing rate of 12K/min with a constant flow of air (60mL/ chemicals industry also. This tendency is helped by the min). H-Mordenite (Si/Al = 19) was a product of Zeo- availability of novel catalytic materials and modern lyst International, USA. K-10 montmorillonite clay techniques of creating and investigating specific active was purchased from Sigma–Aldrich USA. SiO2 was pre- sites on catalyst surfaces. pared in the laboratory by well-known procedures re- Solid acid catalysts pose a good substitute for such ported in literature [26]. Aldoximes were prepared by reactions. The ammoxidation of alkyl aromatics has coupling the corresponding aldehydes (99% benzalde- been employed for long time as a commercial process hyde was a product of SD-Fine Chemicals, India and to produce the corresponding nitrile. Cavani and co- 98% 4-methoxybenzaldehyde also was from the same workers studied the ammoxidation of toluene to benzo- company) with hydroxylamine hydrochloride (99%, nitrile over transition metal modified V2O5 (yield 52%) SD-Fine chemicals, India) in presence of mild base such [13,14]. Recently, Chary and co-workers reported the as NaHCO3 at refluxing temperatures. ammoxidation of toluene to benzonitrile over a series The percentage of metal ion-exchanged and frame- of supported vanadium oxide catalysts under low and work Si/Al ratio were determined by EDX using a JEOL high conversions. The selectivity for benzonitrile re- JSM-840 A (Oxford make model l6211 with a resolution mains almost the same under both conditions. The of 1.3eV). Samples were prepared by dusting the zeolite activities/selectivities in percentage under high conver- powder onto double sided carbon tape mounted on a sion conditions over different supported V2O5 catalysts metal stub. Sensitivity of the instrument was approxi- are 81/93 over V2O5/Nb2O5, 73/87 with V2O5/ZrO2, 67/ mately 2-wt.%. Structural information was obtained 91 on V2O5/TiO2 (anatase), 30/84 V2O5/Al2O3, 16/80 from XRD performed using a Rigaku D-max C X-ray with V2O5/SiO2, and 90/85 over 5% V2O5/TiO2–Nb2O5 diffractometer with Ni-filtered CuKa radiation in the [15,16]. Stobbelaar reported the ammoxidation of tolu- range 5–40° and IR performed using a Nicolet Impact ene over supported metal oxide catalysts and concluded 400FT IR spectrometer in the transmission mode that V/NaY and Mn/NaY catalysts show relatively high (400–4000cmÀ1). The surface area and pore volume mea- benzonitrile yield under optimum conditions [17]. Sanati surements were carried out with the help of a Micromer- et al. reported that the selectivity for benzonitrile forma- itics Gemini surface area analyzer using nitrogen tion increases rapidly with increase in vanadia loading adsorption at liquid nitrogen temperature. Acid struc- B. Thomas et al. / Microporous and Mesoporous Materials 79 (2005) 21–27 23 tural properties were determined by temperature pro- exchange of potassium with
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